Cementitious material and preparation thereof.



- tions UNITED STATES PATENT OFFICE.

" HENRY SPENCER SPAGKMAN, OF ARDMORE, AND ELLIS WARREN LAZELL, OF PHILADEL- PHIA, PENNSYLVANIA, ASSIGNORS TO HENRY S. SPAOKMAN ENGINEERING COMPANY, OF PHILADELPHIA, PENNSYLVANIA, A CORPORATION OF NEW JERSEY.

CEMENTITIOUS MATERIAL AND PREPARATION THEREOF;

Specification of Letters Patent.

Patented Nov. 3, 1908.

Application filed August 29, 1908. Serial No. amass.

To all whom it may concem:

Be it known that we HENRY S. SPAOK-' of Philadelphia, State ofPennsylvania, citizens of the United States, have made certain new and useful Inventions Relating to Cementitious Materials and Preparation Thereof, of which thefollowing is a specification.

This invention relates to cementitious, that is to say, plastic materials or compositions, comprising plasters, hydraulic and other cements and relates more particularly to highly cementitious materials and to the preparation thereof by the incorporation of separately repared calcium aluminate or similar acce crating material with independently cementitious material, such as lime or other similar earthy alkali material or cements or mixtures comprising available lime or similar earthy alkali substance mixed or combined withicoo crating silicious material, such as fine graine hi h silica clays or shales or with natural pozzuo anic material, such as tufa trass, infusorial earth, gaize or with artificial ozzuloanic materials, such as ordina'r b ast furnace sla or specially prepare slag or silicates 0% calcium or other material.

Hydraulic calcium aluminate compounds may be readily pre ared by calcining suitable mixtures of ely ground lime and bauxite or other alumina compounds, such as kaolin or high alumina clays, high alumina slag and so forth, the materials being preferably combined in such proporthat from one to three molecules of hme are present to one molecule of alumina, sufficient lime being of course added to comblue with the silica or other acid components which may be present in connection with the aluminous material added to form the mixture. Such mixed materials may be rendered hydraulic and given a very quick initial set when ground and mixed with water by calcining or cinterin them, and if desired by subsequently fusing them in some cases which seems to give a slower Initial set to aluminates containing approximately equivalent proportions of lime and alumina." It is of course understood that iron or similar material may be used in some cases to replace to some extent at least the alumina in thisaccelerating material, and

that other earthy alkali material, such as magnesia and so forth, may be substituted for art at least of the lime combined there- Witll: such calcium aluminates and e uivalent or substitute accelerating material eing designated hydraulic earthy alkali acceleratm% comfpounds of alumina-like material.

uita le proportions of hydraulic calcium aluminate or similar accelerating material and also if desired controlling material to effect the desired quickness of set and increase of strength ma be added and incorporated at any t1me be ore utilization with the independently cementitious material com rising oxids, hydrates or otherwise availab e lime or similarly acting earthy alkali material combining or capable of combining with hydraulic calcium aluminate and cooperating silicious material. The finely diwided accelerating material maybe added and incorporated by the workman before or after he ages the cementitious material, or it may be dissolved or incorporated in the gaging water; preferably however the accelerating and controlling material may be uniformly incorporated with the independently cementitious material so as to form a finely ground material convenient for transportation and utilization since it becomes immediately effective when the water is added thereto. Such aluminates, besides being hydraulic and strongly cementitious, form' hydraulic cementitious materials of considerable strength when lime or equivalent cementitious earthy alkali material is incorporated therewith up to seventy per cent. or more; also many other cementitious substances may be made more quick setting, more strongly hydraulic and stronger especially at short periods by Incorporating therewith suitable small proportions of h draulic calcium aluminate or similar acce erating material. Many natural, Portland, pozzuolanic and slag cements ma with adxantage receine a suitable addition of this preiously" repared accelerating material, from two to live percent. being usually sufiicient for such purposes to ive a very considerable increase in uic ness of set and stren th, especially w on similar proportions o a' ailable lime are added or are present. Desirable cements of this character for ordinary purposes may comprise seventy to ninety per cent. of the ori inal cement, ten to twenty per cent. of h g alkali materia (that is, free or loosely combined lime, magnesia, baryta, strontia and other material capable of combining with co- 0 erating silicious material and calcium a uminate accelerating material) with which three to seven per cent. of the previously prepared hydraulic calcium aluminate accelerating material and one to three per cent. of calcium sulfate controllin material have been incorporated, an initial set as quick as fifteen minutes or as slow as several hours being thus attainable as desired. The incorporation of five to ten per cent. of cal cium aluminate accelerating material, and if desired, up to five or ten per cent. of hydrated lime and one to three per cent. of calcium sulfate with independently cementitious material such as the low-limed natural cements of the Lehi h district gives very good compositions an causes very considerable increases in their sand strengths, es

pecially at early periods.

As an illustration a composition containing ninety per cent. of such natural cement giving when tested with three parts of sand about 100 poundsat seven days and about 140 ounds at twenty-eight days and having the ollowing approximate composition with which was incorporated ten per cent. of hydraulic calcium aluminate accelerating material having the following approximate composition Natural A ccelercement. ator.

SLO 22. 82 1. 16 R10: 10. 76 66. 92 03.0 48.40 31.46 g0 1. 52 72 Loss on ignition 13. 72 .02

gave when tested in accordance with the standard methods the followmg results: m1- tial set two hours andthirty minutes; final set four hours and fifty minutes; tensile strength with three arts of. sand at seven days 160 pounds, an at twenty-eight days 230 pounds. Another compositlon made from materials of ap roximately the same analyses incorporate in proportions of e' htyper cent. of natural cement ten percent. ydrated lime, seven per cent. of h drauhc calcium aluminate acce erator and t ree per cent. calcium sulfate gave the following tests: initial set one hour fifty-five minutes;

final set four hours; tensile strength with cium aluminate accelerator and three parts of standard sand at seven days 210 pounds and at twent -ei ght days 380 d s. Another natur cement som what more finely round when ninety 'arts were incorporate .with five parts 0 hydrated lime and five parts of hydraulic caltested with rated lime or other earthy drau three parts of sand gave at one day 210 ounds and at seven days 360 pounds. hese compositions are also constant in volume when tested in steam and hot water,

thus as indicated fulfilling the constant volume and sand strength re uirements for standard Portland cement. he incorporation of a considerably larger proportion, such as ten to twenty-five per cent. or more of calcium aluminate accelerating material,for instance, to such cements containing available lime or the like or having the same added thereto produces cements having much greater strengths with sand than the original cements. Various proportions of such accelerating material may also be incorporated with mixtures of slak'ed lime or its equivalent and silicious clay or shale or pozzuolanic material (preferably either fine grained or finely ground so that ninety-five er cent. or so pass a sieve having a hundred meshes to the linear inch) to secure the desired quickness of set and increase of strength, the percentage to be added dependin of course on the chemical composition of t e in redients used two to ten per cent. of calcium a uminate being usually suificient, it not having been found necessary to add much over twent per cent. to produce cements e ual in strengtli ,when used with sand to Port and cements; although considerably larger proportions of the accelerator give much greater strength to the cement at early eriods, the aluminate when gaged alone or a ter incor oration with small proportions of lime an cooperating silicious material iving strengths considerably in excess of l ortland cement. Such a com osition as eighty-five per cent. of hy- 0 calcium aluminate accelerator formed bly calcining about two parts of lime and t ree parts of alumina incorporated in finely divided condition with ten per cent. of hydrate of lime and five per cent. of calcium sulfate, and compositions containing thirtyfive to forty-five per cent. of such calcium aluminate accelerator and forty-five to fifty-' five per cent. or so of Portland or natural cement, for example, seven per cent. of hydrate of lime and three per cent. of calcium sulfate show very great strengths especially at short periods. A good illustrative composition f or use as ordinary hydraulic cement may be secured by mixing approximately forty-five parts of h drated lime, forty-five parts of natural sha e or clayor of pozzuolanic material, and ten parts of the calcium aluminate material, from one to three er cent of plaster of paris being added to this mixture to contro the rate of setting. The proportionsof materials may be varied within a wide range without effecting materially the results and are subject to some modification for each special material. Good hydraulic compositlons can be obtained in some cases with a lime content as high as about eighty per cent.

or containing as low as about fifteen per cent.

or even less of free or availablelime when the Silica sio, Alumina and iron oxid (R 0 42% Calcium hydrate (Ca(OH),), 96.87%

forty-five parts of clay having the following approximate analysis:

Silica (SiO,) 69. 02% Alumina (A1 0 5.31% Iron oxid(Fe,O 2 7 Lime (CaO) 6 22% Magnesia (MgO) 31 12 Loss on ignition 11. 96%

seven parts of hydraulic calcium aluminate accelerating material and three parts of plaster of paris. This material when the components were thoroughly incorporated by being ground together so that ninety-five per cent. passed through a IOU-mesh sieve had,

when gaged with water, an initial setting time of about two hours and was completely set in about four hours according to the indications of the standard Vicat needle. A sample of this hydraulic highly cementitious material, when tested at the twenty-eight day period in the ordinary way with three parts of commercial sand in water gave tensile strengths equal to those obtained from Portland cements, and the material passed the standard soundness or constanc of VOlume test in boiling waterspecified or Portland cement, indicating that it has cementitious properties similar to Portland cement. Suitab epozzuolanic material such as voloanic earths, tufa,- slag and so forth are par- *ticularly adapted to the making of cement by this rocess. Many such materials when mixer with lime or other earthy alkali material and incorporated with from five to ten per cent. of calcium aluminate as indicated, develop their set in a few hours and show tensile strengths when tested with sand equal to those obtained from Portland cements at seven and'twenty-eight days and longer periods; thus they are radica ly different from thewell known pozzuolanie cements formed by the addition of lime alone to such material and being so undesirable because of their slow setting, poor sand carrying and other objectionable properties. 7

Other cementitious or plast c materials may be formed by the incorporation of acomparatively small proportion of calcium aluminate accelerating material with a; large roportion of lime orsimllaralkali material, t ese thoroughly grinding them together.

compositions being especially desirable for use as wall plaster or for similar purposes, and since for these purposes the material can harden in air its hydraulic properties are comparatively unimportant. A good composition for use as commercial wall plaster may be secured by adding such an amount of the accelerator as to have from one to ten per cent. of alumina present, according to the quickness of set desired, the materials being also in this case preferably incorporated by The hardness and strength of plastic, that is to say, cementitious materialof this character can apparently be increased by the incorporation of a suitable proportion of silicic or pozzuolanic material, from one to about ten per cent. for instance, and it is of course also desirable to add from one to five per cent. of plaster of paris, gypsum, glue, starch, molasses, or other controlling material to regulate the setting time.

A desirable composition for general use as wall plaster may be prepared by incorporating eighty-six arts of dry hydrated lime, ten parts of ca cium aluminate accelerating material containing approximately forty per cent. of alumina, two parts of plaster of paris and two parts of infusorial earth. This material when the components are thoroughly incorporated and finely ground together so that ninety-five per cent. pass through a 100- mesh sieve has an initial setting time of about four hours and is completely set in about fifteen hours according to the standard Vicat needle test. 4 titious material when tested in t e ordinary way with three parts of commercial sand in air gives the following high tensile strengths: at seven days 125 pounds per square inch and at twenty-ei ht days 151 pounds per square inch. A p aster composition having A sample of this hi hly cemen-.

less tensile strength and therefore being more desirable as a general wall finish in building operations may be similarly prepared by incorporating eighty-eight arts of dry hydraterLlime, seven parts of ydraulic calcium aluminate accelerating material containing a proximately forty per cent. of alumina, t ree parts of plaster of Paris and two parts of basic blast furnace slag. This plaster material when tested in the ordina Way with three parts of commercial sand in air gives about fifty pounds tensile strength per square inch at seven days and about ninety pounds at twenty-eight days. When used as a plaster as much as five parts of commercial sand can be readily incorporated therewith and give the desired spreading qualities for Wall finishing, the pl'aster hardeningcompletely so as to allow the ap lication of a finishing coat in about twelve ours.

Having described the invention in this cas which is a. continuation of, that is, contains isu'bject-matter taken from United States patent application, 394,916, filed September 27, 1907, in connection with a number of illustrative ingredients, proportions, formulas and methods of preparation, to the details of which disclosure the invention is not of course to be limited, what is claimed as new and what is desired to be secured by Letters Patent is set forth in the appended claims.

1. The hydraulic highly cementitious material fulfilling the constant volume requirements for standard. Portland cement and having considerably greater strength at early periods than standard Portland cement comprising available lime and up to about fifty per cent. of separately repared hydraulic calcium aluminate acce crating material. with which controlling material and hydraulic independently cementitious material are incorporated.

2. The hydraulic highly cementitious material fulfilling the constant volume requirements for standard Portland cement and having considerably greater strength at early periods than standard Portland cement comprising available earthy alkali material and up to about fifty per cent. of separately prepared hydraulic earth alkali accelerating compounds rich in alumina-like material with which controlling material and hydraulic independently cementitious material are incorporated.

3. The highly cementitious material fulfillin the constant volume re uirements for stan ard Portland cement an having con siderably greater sand strength at early periods than standard Portland cement comprising available lime and considerable proportions of separately prepared hydraulic calcium aluminate accelerating material with which controlling material and independently cementitious material are incorporated.

4. The highly cementitious material having considerably greater sand strength at early periods than standard Portland cement comprising available earthy alkali material and considerable proportions of separately prepared hydraulic earthy alkali acceleratin compounds rich in alumina-like materizil with which cooperating cementitious material and controlling material are incorporated.

5.. The highl cementitious material having considerab y greater sand strength at early periods than standard Portland cement comprising considerable proportions of prepared hydraulic earthy alkali accelerating compounds rich in alumina-like material with which-cooperating cementitious material is lnco orated.

he highly cementitious material having co-nslderab y greater strength at early periods than standard Portland cement comprising considerable proportions of hydraulic calcium aluminate material with which 00* operating cementitlous material is incorporated.

8. The hy raulic highly cementitious material fulfilling the constant volume and sand strength requirements for standard Portland cement comprising considerable proportions of lime and cooperating silicious material and comprising a small percenta e of incorporated separately prepared hy raulic calcium aluminate accelerating material and calcium sulfate controlling material.

9. The highly cementitious material fulfillin the constant volume and sand strength requirements for standard Portland cement comprising large proportions of earthy alkali material and cooperating silicious material and comprising a small percentage of incorporated hydraulic calcium aluminate accelerating material and controlling material.

10. The hydraulic highly cementitious material fulfilling the constant volume and sand strength re uirements for Portland cement comprising arge proportions of lime and cooperating silicious material and comprising a small proportion of incorporated separately prepared ydraulic calcium aluminate acceleratin material.

11. The hydraulic highly cementitious mastrength requirements for Portland cement comprising large proportions of lime and cooperating silicious material and comprising a small percentage of incorporated separately prepared hydraulic earthy alkali accelerating compound of alumina-like material and controllmg material.

13. he hydraulic highly cementitious material fulfilling the constant volume and sand strength requirements for Portland cement com rising considerable proportions of earthy alka i material and cooperating silicious material and comprising a small percenta e of separately prepared h draulic earthy a kali accelerating com oun s of alumina-like material and contro ling material.

14. The gfildrauhc highly cementitious material to] 'ng the constant volume and sand strength requirements for Portland cement comprising large proportions of lime and cooperating silicious material and comprising a small percentage of incorporated separately prepared h draulic earthy alkali accelleratrng compound s of alumina-like ma teria 15. The hydraulic highly cementitious material fulfilling the constant volume and sand strength requirements for Portland cement com rising considerable proportions ofearthy alka material and cooperating silicious material and comprisingl a small percentage of separately prepared ydraulic earthy alkali accelleratmg compounds of alumina-like materia.

16. The hydraulic highly cementitious material fulfilling the constant volume and strength requirements for standard Portland cement comprising a large proportion of hydraulic independently cementitious material and comprising a small percentage of incorporated separately prepared calcium aluminate accelerating material and controlling material.

17. The hydraulic highly cementitious material fulfilling the constant volume and sand strength requirements for standard Portland cement comprising a large proportion of hydraulic independently cementitious material and comprising a small proportion of available lime and of separately pre ared calcium aluminate accelerating materia 18. The hydraulic highly cementitious material fulfilling the constant volume and strength requirements for standard Portland cement com risin a large'proportion of hydraulic inepen ently cementitious material and comprising a small proportion of incorporated separately prepared hydraulic earthy alkali acceleratin compounds rich in alumina-like materia and of controlling material.

19. The hydraulic highly cementitious material fulfilling the constant volume and strength requirements for standard Portland cement comprising a large proportion of hydraulic independently cementitious material and comprising a small pro ortion of incorporated separately prepared draulic earthy alkali accelerating compoun s rich in, alumina-like material.

.20. The hydraulic highly cementitious material comprising a' large proportion of independently cementitious material comprising lime with which a small proportion of separately prepared hydraulic calcium aluminate acce crating material is incorporated to increase the V uickness of set and early tensile strength of t e material.

21. The hydraulic highly cementitious material com risin independently cementitious materi wit which separately pre ared hydraulic calcium aluminate acceleratmg material is incorporated to increase the uickness of set and early tensile strength of t e material.

22. The highly cementitious material comprising a large proportion of inde endentl cementitious material comprising ime wit which a small proportion of separately prepared hydraulic earthy alkali accelerating compounds rich in alumina-like material is incorporated to increase the quickness of set of the material.

23. The highly cementitious material comprising independently cementitious material comprising earthy alkali material with which a small proportion of separately prepared hydraulic earthy alkali acceleratin compounds rich in alumina-like materia is incor orated toincl'ease the quickness of set of t e material.

24. The hydraulic highly cementitious material comprising a large proportion of earthy alkali material and com rising incorporated separately prepared by raulic calcium aluminate acce crating material to increase the uickness of set and early tensile strength of t e material.

25. The hydraulic highly cementitious material comprising a large proportion of earthy alkali material and comprising incorporated separately prepared hydraulic earthy alkali acceleratin compounds rich in alumina like materia to increase the uickness of set and early tensile strength of t e material.

26. The process of preparing highly cementitious material which consists in calcining calcium alumina compounds to form hydraulic calcium aluminate accelerating material and in incor orating a considerable proportion thereo with independently cementitious material comprising available lime to produce hydraulic highly cementitious material having strengths considerably in excess of Portland cement at early eriods.

27. The process of preparing highly cementitious material which consists in incorporating considerable pro ortions of separately pre ared hydrau ic calcium aluminate acce crating material with hIydraulic independently cementitious materia to pro-.

duce hydraulic highly cementitious material having strengths considerably in excess of Portland cement at early periods.

- 28. The process of pre aring highlycementitious material Whic corporating se arately prepared calcium aluminate acce crating material with independently cementitrous material comprlsing available earthy alkali material to produce highly cementitious material having considerably greater sand strengths at early periods than standard Portland cement.

29. The process of preparing highly cementitious material which consists in incorconsists in in-' porating considerable roportions of separately prepared hydrau c earthy alkali acceleratmg compounds .rich in alumina-like material with cooperating cementitious material to reduce cementitious material having consi erably greater sand stren he at ear y periods than standard Portlan cement.

30. The process of preparing highly cementitious material which consists in incorporating separately prepared calcium aluminate accelerating material with independently cementitious material comprising available lime to increase the quickness of set and early strength of the material.

31. The process of preparing highly cementitious material which consists in incorporating separately prepared calcium aluminate accelerating material and controlling material with independently cementitious material comprising lime and cooperating silicious material.

32. The process of preparing highly cementitious material which consists in incorporatin separately prepared hydraulic calcium a uminate accelerating material and calcium sulfate controlling material with independently cementitious material comprising lime.

33. The process of preparing highly cementitious material which consists in incor porating separately prepared hydraulic earthy alkali compounds rich in alumina-like material and controlling material with independentl cementitious material comprising earthy alkali material.

34. The process of preparing cementitious material which consists in incorporating se arately prepared calcium aluminate acce eratin material and controlling material with in ependentl cementitious material comprising availab e lime.

35. The process of preparing cementitious material which consists in incorporating separately prepared hydraulic calcium aluminate accelerating materiaLwith independently cementitious material comprising hydrated lime to increase the quickness of set and earl strength of the material.

36. T e process of preparing cementitious material w 'ch consists in incorporating at least a small proportion of separately prepared hydrauhc calcium alummate accelerating material and calcium sulfate controlling material with independently cementitious material comprising hydrated lime to increase the quickness of set, early strength and spreading properties of the material.

celerating material and incorporated calcium sulfate controlling material.

38. The regulating material for use with cementitious material comprising earthy al kali material which comprises hydraulic calcium aluminate accelerating material and incorporated controlling material.

39. The regulating material for use with cementitious material comprising earthy alkali material which comprises hydraulic earthy alkali accelerating compounds rich in alumina-like material and incorporated calcium sulfate controlling material.

40. The regulating compound for use with cementitious material comprising earthy alkali material which consists of hydraulic earthy alkali accelerating compounds of alumina like material and incorporated control ling material.

41. The process of preparing highly cementitious material which consists in incorporating separately prepared calcium aluminate accelerating material with hydraulic independentl cementitious material comprising availab e lime to increase the quickness of set and early strength of the material.

42. The process of preparing highly cementitious material which consists in incor porating separately prepared earthy alkali accelerating compounds rich in alumina-like material with hydraulic independently cementitious material comprising lime and cooperating silicious material. 43. The process of preparing highly cementitious material which consists in incorporating separately prepared hydraulic earthy alkali compounds rich in alumina-like material and controlling material with hydraulic independentl cementitious material comprising earthy al ali material.

HENRY SPENCER SPACKMAN. ELLIS WARNER LAZELL.

Witnesses:

Loors F. SCHUGK,

W. L. WILSON. 

